This invention relates to a gas-phase dehydration reaction process of a hydroxyl group-containing compound. More detailedly, the invention relates to an improvement in a gas-phase dehydration reaction process of a hydroxyl group-containing compound using a solid oxide catalyst containing an alkali metal element.
Known as examples of a process of carrying out gas-phase dehydration reaction of a hydroxyl group-containing compound using a solid oxide catalyst containing an alkali metal element are a process of preparing a cyclic amine by gas-phase intermolecular dehydration of an alkanolamine (Japanese Laid-open Patent Publication No. 126556/88, etc.), a process of preparing an unsaturated ether by gas-phase intermolecular dehydration of a glycol ether (Japanese Laid-open Patent Publication No. 143497/96, etc.), a process of preparing an N-alkenylcarboxylic acid amide by gas-phase intermolecular dehydration of a tertiary N-(2-hydroxyalkyl)carboxylic acid amide (Japanese Laid-open Patent Publication No. 141402/96, etc.), a process of preparing an alkylene sulfide by gas-phase intermolecular dehydration of a mercaptoalkanol (Japanese Laid-open Patent Publication No. 202027/93, etc.), a process of preparing a tertiary amine compound by gas-phase intermolecular dehydration of a secondary amine compound and an alcohol (Japanese Laid-open Patent Publication No. 241220/97, etc.), a process of preparing an alkyl ether of a phenol by gas-phase intermolecular dehydration of the phenol and an alcohol (Japanese Laid-open Patent Publication No. 235248/97, etc.).
Hydroxy group-containing compounds as raw materials of the gas-phase dehydration reaction, particularly alkanolamines, glycol ethers and hydroxyethyl compounds such as N-(2-hydroxyalkyl)carboxylic acid amides have a hydroxyl group and an amino group or an amido group or an ether group in the molecule and thermally unstable, and when they contact with an acidic substance at high temperature, decomposition reaction takes place to form acetaldehyde, ethanol and high boiling products. Further, unsaturated ethers, N-alkenylcarboxylic acid amides and cyclic amines as the objective products have a high reactivity and are liable to cause polymerization, formation of high boiling substances, etc. Such reaction would lead not only to a decrease in the reaction yield but also to an increase in the costs for the recovery and purification of the raw materials and the products.
Therefore, in order to put the gas-phase dehydration reaction into an industrial practice, it is important to heat the raw material gas vaporized in the vaporator up to a predetermined temperature without deteriorating it inside the heater (gas preheater) and/or at the inlet side of the catalyst layer in the reactor, and immediately feed it into the catalyst layer, and immediately cool the reaction gas which came out of the catalyst layer.
When the gas-phase dehydration reaction is carried out using a fixed bed reactor, the catalyst needs to be supported by some supporting material for fixing the position of the catalyst. In this occasion, it is important to prevent deterioration of the raw materials and the products on the catalyst supporting material.
However, the above-mentioned official bulletins only describe catalysts capable of converting the raw materials into the objective products selectively at a high space time yield, and they do not describe a process of preheating the raw material gas, a process of cooling the reaction gas and a process of supporting the catalyst at all.
On the other hand, Japanese Patent Publication No. 40792/72 discloses a reaction process comprising gas-phase intermolecular dehydration of N-(2-hydroxyethyl)-2-pyrrolidone to prepare N-vinyl-2-pyrrolidone. This prior art publication discloses loading Raschig rings (outside diameter 5 mm, length 5 mm, porcelain) as an evaporation preheating band of the raw material into the upper part of a vertical stainless steel reaction tube, loading an oxide of zirconium or thorium as a catalyst into a reaction band of the lower part thereof and carrying out gas-phase dehydration reaction. However, it does not disclose decomposition of the raw material at the evaporation preheating band and the composition of the porcelain Raschig ring. Further, Raschig rings for general purposes have problems, for example, that since they have an outside diameter of as large as 4 mm or more and a void ratio of as large as 0.6 to 0.9, they are liable to cause thermal denaturation of the raw material and cannot be used as a supporting material of catalysts having a small particle size.
The object of the invention lies in providing, in a gas-phase dehydration reaction process of a hydroxyl group-containing compound using a solid oxide catalyst containing an alkali metal element, the improvement which makes it possible to inhibit decomposition of the raw materials and the objective products thereby to carry out the gas-phase dehydration reaction efficiently.
The present inventors have intensively studied in order to provide a gas-phase dehydration reaction process capable of solving the above problems, and as a result, they have found that the stability of the raw materials used in the reaction is strikingly influenced not only by the catalyst itself, but by the composition of a loading material for preheating of the raw material gas as well as the composition of a supporting material for fixation of the position of the catalyst.
Thus, the invention provides, a process of gas-phase dehydration reaction comprising contacting a raw material gas with a solid oxide catalyst containing an alkali metal element, wherein a sintered oxide comprising an alkali metal element and silica and/or alumina is used as a loading material for preheating of the raw material gas and/or as a supporting material for fixation of the position of the catalyst.
The invention is particularly useful when the solid oxide catalyst is a solid oxide containing an alkali metal element and silicon.
In the invention, the sintered oxide is preferably a sintered oxide obtained by adding a compound containing an alkali metal element to a sintered oxide comprising an alkali metal element and silica and/or alumina, followed by calcining the mixture.
The invention is useful when the raw material of the gas-phase dehydration reaction is a hydroxyethyl compound represented by the following general formula (I)
Z1xe2x80x94CH(R1)xe2x80x94CH(R2)xe2x80x94OHxe2x80x83xe2x80x83(I) 
[wherein Z1 is an amino group, a monoalkylamino group having 1 to 6 carbon atoms, a mercapto group, an alkoxy group having 1 to 10 carbon atoms, an alkylcarboxylic acid amido group wherein the alkylcarboxylic acid moiety has 1 to 6 carbon atoms and the group binding to the N atom of the amido moiety is a hydrogen atom or a methyl group, or a cyclic carboxylic acid amido group including an alkylene group having 3 to 5 carbon atoms and R1 and R2 are each, independently, a hydrogen atom, a methyl group or an ethyl group].
Further, the invention is particularly useful when the gas-phase dehydration reaction is a reaction comprising gas-phase inter-molecular dehydration of a hydroxyethyl compound represented by the following general formula (II)
Z2xe2x80x94CH2xe2x80x94CH2xe2x80x94OHxe2x80x83xe2x80x83(II) 
[wherein Z2 is an alkoxy group having 1 to 10 carbon atoms, an alkylcarboxylic acid amido group wherein the alkylcarboxylic acid moiety has 1 to 6 carbon atoms and the group binding to the N atom of the amido moiety is a hydrogen atom or a methyl group, or a cyclic carboxylic acid amido group including an alkylene group having 3 to 5 carbon atoms]
to convert it to a vinyl compound represented by the following general formula (III)
Z2xe2x80x94CHxe2x95x90CH2xe2x80x83xe2x80x83(III) 
[wherein Z2 is as defined in the formula (II)].
Further, the invention is particularly useful when the gas-phase dehydration reaction is a reaction comprising gas-phase inter-molecular dehydration of a hydroxyethyl compound represented by the following general formula (IV)
R3xe2x80x94NHxe2x80x94CH2xe2x80x94CH2xe2x80x94OHxe2x80x83xe2x80x83(IV) 
[wherein R3 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms]
to convert it to a cyclic amine represented by the general formula (V) 
[wherein R3 is as defined in the formula (IV)].
The invention is detailedly described below.
The invention is an improvement process applied to a gas-phase dehydration reaction comprising contacting a hydroxyl group-containing compound as a raw material gas with a solid oxide catalyst containing an alkali metal element, preferably a solid oxide catalyst containing an alkali metal element and silicon.
As specific examples of the solid oxide catalyst containing an alkali metal element, when represented by compositions excluding oxygen, there can be mentioned Lixe2x80x94Si, Naxe2x80x94Si, Kxe2x80x94Si, Rbxe2x80x94Si, Csxe2x80x94Si, Naxe2x80x94Al, Naxe2x80x94Zr, Lixe2x80x94Sixe2x80x94P, Naxe2x80x94Sixe2x80x94P, Kxe2x80x94Sixe2x80x94P, Rbxe2x80x94Sixe2x80x94P, Csxe2x80x94Sixe2x80x94P, Naxe2x80x94Mgxe2x80x94Si, Lixe2x80x94Sixe2x80x94Al, Naxe2x80x94Kxe2x80x94Si, Naxe2x80x94Csxe2x80x94Si, Csxe2x80x94Sixe2x80x94Zr, Kxe2x80x94Sixe2x80x94Nb, Kxe2x80x94Sixe2x80x94Alxe2x80x94P, Rbxe2x80x94Sixe2x80x94Alxe2x80x94P, Csxe2x80x94Sixe2x80x94Alxe2x80x94P, Rbxe2x80x94Sixe2x80x94Zrxe2x80x94P, etc., but the invention should not be limited thereto.
As gas-phase dehydration reactions to which the invention is applicable, there can be mentioned various gas-phase dehydration reactions such as a vinylation reaction by intramolecular dehydration of a hydroxyethyl compound, a cyclization reaction by intramolecular dehydration of a hydroxyethylamine, an etherification reaction by intermolecular dehydration between a phenol and an alcohol, and an N-alkylation reaction by intermolecular dehydration between an amine or an amide and an alcohol. However, the invention should not particularly limited to such reactions.
The process of the invention is particularly useful when the raw material of the gas-phase dehydration reaction is a hydroxyethyl compound represented by the following general formula (I)
Z1xe2x80x94CH(R1)xe2x80x94CH(R2)xe2x80x94OHxe2x80x83xe2x80x83(I) 
[wherein Z1 is an amino group, a monoalkylamino group having 1 to 6 carbon atoms, a mercapto group, an alkoxy group having 1 to 10 carbon atoms, an alkylcarboxylic acid amido group wherein the alkylcarboxylic acid moiety has 1 to 6 carbon atoms and the group binding to the N atom of the amido moiety is a hydrogen atom or a methyl group, or a cyclic carboxylic acid amido group including an alkylene group having 3 to 5 carbon atoms and R1 and R2 are each, independently, a hydrogen atom, a methyl group or an ethyl group].
As specific examples of the hydroxyethyl compound of the general formula (I), there can be mentioned 2-aminoethanol, 2-(ethylamino) ethanol, N-(2-hydroxyethyl)-2-pyrrolidone, N-(2-hydroxyethyl)-acetamide, N-(2-hydroxyethyl)-formamide, 2-methoxyethanol, 2-ethoxyethanol, 2-isopropoxyethanol, n-propoxyethanol, 2-butoxyethanol, 2-isobutoxyethanol, 2-(2-ethylhexyloxy)ethanol, 2-(2-ethoxyethoxy) ethanol, 2-(2-butoxyethoxy)ethanol, 2-(2-(2-ethoxyethoxy)-ethoxy)ethanol, diethylene glycol, triethylene glycol, etc.
Further, the process of the invention is particularly useful when the gas-phase dehydration reaction is a reaction comprising gas-phase intermolecular dehydration of a hydroxyethyl compound represented by the following general formula (II)
Z2xe2x80x94CH2xe2x80x94CH2xe2x80x94OHxe2x80x83xe2x80x83(II) 
[wherein Z2 is an alkoxy group having 1 to 10 carbon atoms, an alkylcarboxylic acid amido group wherein the alkylcarboxylic acid moiety has 1 to 6 carbon atoms and the group binding to the N atom of the amido moiety is a hydrogen atom or a methyl group, or a cyclic carboxylic acid amido group including an alkylene group having 3 to 5 carbon atoms]
to convert it to a vinyl compound represented by the following general formula (III)
Z2xe2x80x94CHxe2x95x90CH2xe2x80x83xe2x80x83(III) 
[wherein Z2 is as defined in the formula (II)].
As specific examples of the hydroxyethyl compound of the general formula (II), there can be mentioned N-(2-hydroxyethyl)-2-pyrrolidone, N-(2-hydroxyethyl)-acetamide, N-(2-hydroxyethyl)-formamide, 2-methoxyethanol, 2-ethoxyethanol, 2-isopropoxyethanol, n-propoxyethanol, 2-butoxyethanol, 2-isobutoxyethanol, 2-(2-ethylhexyloxy) ethanol, 2-(2-ethoxyethoxy)ethanol, 2-(2-butoxyethoxy)-ethanol, 2-(2-(2-ethoxyethoxy)ethoxy)ethanol, diethylene glycol, triethylene glycol, etc.
As specific examples of the vinyl compound of the general formula (III), there can be mentioned N-vinyl-2-pyrrolidone, methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, ethylene glycol monovinyl ether, diethylene glycol monovinyl ether, etc.
Further, the process of the invention is particularly useful also when the gas-phase dehydration reaction is a reaction comprising gas-phase intermolecular dehydration of a hydroxyethyl compound represented by the following general formula (IV)
R3xe2x80x94NHxe2x80x94CH2xe2x80x94CH2xe2x80x94OHxe2x80x83xe2x80x83(IV) 
[wherein R3 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms]
to convert it to a cyclic amine represented by the general formula (V) 
[wherein R3 is as defined in the formula (IV)].
As specific examples of the hydroxyethyl compound of the general formula (IV), there can be mentioned 2-aminoethanol, 2-(methylamino)ethanol, 2-(ethylamino)ethanol, etc.
As specific examples of the cyclic amine of the general formula (V), there can be mentioned ethyleneimine, N-methylethyleneimine, N-ethylethyleneimine, etc.
The characteristic of the gas-phase dehydration reaction process of the invention lies in using a sintered oxide comprising an alkali metal element and silica and/or alumina as a loading material for preheating of the raw material gas and/or as a supporting material for fixation of the position of the catalyst in the gas-phase dehydration reaction.
Since the sintered oxide of the invention contains silica and/or alumina and an alkali metal element, the sintering step for obtaining an inert sintered oxide is shortened to realize a reduction in the costs, and moreover, it enables to eliminate unnecessary acid sites which accelerate decomposition of the reaction raw materials. Further, the sintered oxide of the invention is characteristics in that it does not accelerate decomposition of the raw material and the objective product and it does not poison the solid oxide catalyst containing an alkali metal element.
The sintered oxide is a sintered oxide comprising an alkali metal element such as sodium, potassium or cesium and silica and/or alumina.
The sintered oxide may contain an impurity such as an alkaline earth metal (e.g., calcium, magnesium, etc.), iron or titanium. However, since such an impurity may increase unnecessary acid sites or lower the strength of the sintered oxide, the total content of the alkali metal element and silica and/or aluminum metal element in the sintered oxide is made to be usually 80% by weight or more, preferably 95% by weight or more, more preferably 98% by weight or more in terms of its oxide.
The content of the alkali metal element in the sintered oxide is not particularly limited; however, for example, 0.5 to 10% by weight, preferably 2.0 to 8.0% by weight in terms of its oxide. When the content of the alkali metal element is less than 0.5% by weight, the sintering temperature rises, and when it is more than 10% by weight, the loading material becomes strongly basic, which may cause decomposition, condensation, etc. of the raw material and/or the objective product.
The content of silica or alumina in the sintered oxide is not particularly limited; however, for example, 10% by weight or more, preferably 30 to 95% by weight, more preferably 50 to 90% by weight in terms of its oxide.
Above all, a silica-alumina sintered oxide containing 2 to 8% by weight an alkali metal and 10 to 90% by weight silica is preferred. The reason of the preference is that silica-alumina wherein the amounts of the alkali metal element and silica are adjusted to the above range is inactivated at a lower sintering temperature and becomes a sintered oxide having a higher strength, compared with a raw material for a sintered oxide having a higher alumina purity.
Processes for preparing the sintered oxide are not particularly limited, and any processes per se known can be applied. As examples thereof, the following processes can be mentioned.
(1) A process comprising kneading an oxide, hydroxide or carbonate between silicon and/or an aluminum metal element and an alkali metal element together with a binder such as water, an alcohol, an organic acid or a polymer, drying and molding the kneaded matter, and then sintering the molded matter.
(2) A process comprising kneading a clay mineral containing silicon and/or an aluminum metal element such as smectite, montmorillonite, bentonite, kaolin or sericite, and a hydroxide of an alkali metal together with a binder such as water, an alcohol, an organic acid or a polymer, molding and drying the kneaded matter, and then sintering the dried matter.
(3) A process comprising adding commercially available molded alumina, silica-alumina or silica to an aqueous solution of an alkali metal element, making impregnation progress for several hours, drying the resulting matter, and then sintering the dried matter.
The sintering temperature in preparation of the sintered oxide is varied depending on the contents of the alkali metal element and silicon and/or the aluminum metal element, but is usually 800 to 1,500xc2x0 C., preferably 900 to 1,300xc2x0 C. When the sintering temperature is lower than 800xc2x0 C., it is difficult to obtain a sufficiently inert sintered oxide, and when it is higher than 1,500xc2x0 C., the time needed for the sintering step may become longer, and moreover, the step may cost a great deal.
As a further preferred process of preparing the sintered oxide, there can be mentioned a process comprising adding a compound containing an alkali metal element to an oxide comprising an alkali metal element and silica and/or alumina and sintered at 800 to 1,500xc2x0 C., followed by calcining the mixture at 400 to 1,000xc2x0 C. According to this process, unnecessary acid sites disappear completely to give a completely inert sintered oxide. As a process for addition of the compound containing an alkali metal element, every known process can be applied. However, preferred is a process comprising impregnating the above sintered oxide comprising an alkali metal element and silica and/or alumina with an aqueous solution of a hydroxide, carbonate or nitrate, particularly preferably hydroxide of an alkali metal element. The concentration of the aqueous solution of an alkali metal element can appropriately be selected, but in the case of the hydroxide, it is 0.1 to 5.0% by weight.
The shape of the sintered oxide used in the invention is varied depending on models and operation conditions of the heater (gas preheater), the reactor and the cooler, but usually, it is spherical or columnar. The size of the sintered oxide is usually in the range of 0.1 to 20 mm, and preferably in the range of 2 to 10 mm.
{circle around (1)} In the case of a heat exchanger type reactor using a heat medium such as an oil or a molten salt, the sintered oxide comprising an alkali metal element and silica and/or alumina of the invention is loaded into the inlet side of the catalyst layer inside the reactor (for example, it is spread on the surface on the catalyst layer).
{circle around (2)} In the case of an adiabatic reactor, the sintered oxide of the invention is loaded inside the heater (gas preheater) connected to the reactor through piping. By thus loading the sintered oxide, the raw material gas is heated to a predetermined temperature without being deteriorated. The sintered oxide, as a loading material, spread on the surface of the catalyst layer also has an effect of preventing the catalyst from moving with the raw material gas and putting the flow of the raw material gas in order.
{circle around (3)} The sintered oxide of the invention can also be used as a supporting material for fixation of the position of the catalyst. For example, when it is loaded as a catalyst-supporting layer into the outlet side of the catalyst layer inside the reactor, it is effective not only for supporting the catalyst, but also for preventing the raw material gas and the reaction gas from being retained and deteriorated.
{circle around (4)} The sintered oxide can further also be used as a loading material in the cooler for immediately cooling the reaction gas of high temperature which came out of the catalyst layer of one of various reactors.
{circle around (5)} Since the sintered oxide is inert to the solid oxide catalyst containing an alkali metal element, it can also be used as a diluent of the catalyst. For example, when reaction heat is large or when carbides, etc. adhering on the catalyst by the reaction are burned, local temperature change due to generation or absorption of heat can be inhibited by using a mixture of the catalyst with the sintered oxide.
The reaction temperature in use of the sintered oxide is usually 200 to 600xc2x0 C., preferably 300 to 500xc2x0 C.
In the process of the invention, a reactor of any model among fixed bed type, moving bed type and fluidized bed type can be used, but preferred is a fixed bed type reactor. As a heat transfer method of the reactor, any method can be applied, and {circle around (1)} a multi-tubular heat exchange method using a heat medium (molten salt, etc.) or {circle around (2)} an adiabatic method wherein there is no heat exchange with the surroundings is particularly preferred.
The reaction pressure in the invention is, usually, ordinary pressure or reduced pressure, but applied pressure is also possible. The reaction temperature is varied depending on the kind of reaction raw materials and other reaction conditions, but is 200 to 600xc2x0 C., preferably 300 to 500xc2x0 C.